US5225560A - Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate - Google Patents
Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate Download PDFInfo
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- US5225560A US5225560A US07/803,855 US80385591A US5225560A US 5225560 A US5225560 A US 5225560A US 80385591 A US80385591 A US 80385591A US 5225560 A US5225560 A US 5225560A
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- pyridinedicarboxylate
- dialkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Definitions
- Pyridine-2,3-dicarboxylates are useful intermediates in the preparation of highly effective herbicidal 2-(2-imidazolin-2-yl)nicotinic acids, esters and salts. Said herbicidal agents and methods for their preparation are disclosed in U.S. Pat. No. 4,798,619 and U.S. Pat. No. 4,758,667. Imidazolinyl nicotinates and derivatives thereof are highly effective herbicides at low rates of application which demonstrate selective control of noxious weeds in the presence of important agronomic crops while exhibiting exceptionally low mammalian toxicity.
- R is C 1 -C 6 alkyl
- X is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or C 2 -C 5 alkenyl
- Z is hydrogen, C 1 -C 4 alkyl or C 2 -C 5 alkenyl
- Y is hydrogen, halogen, C 1 -C 6 alkyl optionally substituted with one to three halogens, hydroxy groups, C 1 -C 4 alkoxy groups or C 1 -C 4 alkylthio groups, C 1 -C 4 alkoxycarbonyl, aminocarbonyl, phenyl, substituted phenyl, phenoxy, substituted phenoxy, phenylthio or substituted phenylthio.
- pyridine-2,3-dicarboxylates of formula I can be efficiently and effectively prepared from dialkyl dichlorosuccinates of formula II by reacting said succinate with at least one molar equipment of a dehydrohalogenating agent such as ammonium acetate or trialkylamine in the presence of a solvent such as a lower alkylalcohol to form an intermediate, reacting said intermediate with a source of ammonia, optionally at elevated temperatures to form a second intermediate and reacting said second intermediate with at least one molar equivalent of an ⁇ , ⁇ -unsaturated aldehyde or ketone of formula III wherein X, Y and Z are as described above for formula I in the presence of an acid such as formic acid or acetic acid or the like.
- a dehydrohalogenating agent such as ammonium acetate or trialkylamine
- a solvent such as a lower alkylalcohol
- Dehydrohalogenating agent suitable for use in the process of the invention are those which may also serve as an ammonia source such as ammonium acetate, ammonium carbonates, ammonium carbamates, ammonium sulfamates and the like. Also suitable are reagents such as trialkylamines, pyridines, picolines, quaternary amine salts such as tetraalkylammonium halides and the like. Of course, in addition to the above-mentioned ammonia sources, ammonia itself may be employed in the process of the invention.
- the solvent utilized may be a polar solvent such as an alcohol, a nitrile such as acetonitrile, a carboxylic acid amide such as N,N-dimethylformamide, N-methylpyrrolidone, a sulfoxide such as dimethylsulfoxide, a sulfone and the like.
- a polar solvent such as an alcohol, a nitrile such as acetonitrile, a carboxylic acid amide such as N,N-dimethylformamide, N-methylpyrrolidone, a sulfoxide such as dimethylsulfoxide, a sulfone and the like.
- ⁇ , ⁇ -unsaturated aldehydes or ketones of formula III which can be used in the process of the invention are acrolein, methacrolein, ethacrolein, crotonaldehyde, methyl vinyl ketone, ⁇ -n-butylacrolein, 4-methyl-2-hexanal, ⁇ -methoxymethacrolein, ⁇ -chloromethacrolein, ⁇ -trifluoromethacrolein, cinnamaldehyde, ⁇ -ethoxyacrolein, methyl ⁇ -formylacrylate, ⁇ -(2-cyanoethyl) acrolein and the like.
- the reaction mixture comprising the above-formed second intermediate and the ⁇ , ⁇ -unsaturated aldehyde or ketone of formula III may be treated with a dehydrogenation catalyst such as that which is conventional in the art including metals or compounds of platinum, palladium, ruthenium, iridium, nickel, iron, copper, antimony, cobalt, rhodium and the like.
- the dehydrogenation catalyst is commonly used in the form of the dehydrogenation metal or compound thereof deposited on a suitable support such as alumina, carbon, clay, zeolite, chromia, zirconia and the like.
- pyridine-2,3-dicarboxylates containing substituents in the 4,5 and 6 positions may be conveniently prepared by admixing a formula II dialkyl dichlorosuccinate with at least one molar equivalent of a dehydrohalogenating agent in a suitable solvent, optionally filtering off insolubles, treating the filtrate or unfiltered reaction mixture with anhydrous ammonia, optionally heating said reaction mixture until the formation of the enamine intermediate is complete, optionally filtering off insolubles, adding to the filtrate or to the unfiltered reaction mixture an acid such as a mineral acid, sulfuric acid, phosphoric acid, an organic acid such as formic acid, acetic acid or propionic acid and the like, and treating with at least one molar equivalent of an ⁇ , ⁇ -unsaturated aldehyde or ketone of formula III optionally adding a dehydrogenation catalyst, optionally heating the resulting reaction mixture until the formation of the formula I pyridinedicarboxylate is complete.
- the desired pyridine-2,3-dicarboxylate can be isolated and purified using conventional methods such as extraction, distillation, recrystallization, chromatography and the like.
- reaction time can be effectively reduced by heating the reaction mixtures at temperatures of about 45° C. or greater.
- a stirred mixture of diethyl dichlorosuccinate (12.2 g, 0.05 mole) and ammonium acetate (15.4 g, 0.20 mole) in absolute ethanol is heated at 60° C. for 6 hours, cooled to 20° C., treated with excess anhydrous ammonia (5.0 g, 0.29 mole), heated at 60° C. for 41/2 hours, partially distilled to remove excess ammonia, cooled to 30° C. and filtered.
- the filter cake is washed with ethanol and the filtrates are combined and concentrated in vacuo.
- the thus-concentrated reaction solution is treated with acetic acid, treated dropwise with an ethanolic solution of 2-ethacrolein at 70° C. over a 11/2 hour period, continued heating at 70° C.
- a solution of diethyl dichlorosuccinate (24.6 g, 0.10 mole) in ethanol is treated with triethylamine (12.2 g, 0.12 mole) over a 5 minute period, allowed to stir at ambient temperatures for 12 hours, treated with anhydrous ammonia (7.3 g, 0.43 mol) at 20° C., heated at 45°-50° C. for 3 hours and filtered.
- the filter cake is washed with ethanol and the filtrates are combined and concentrated in vacuo to remove the solvent and excess ammonia.
- the resultant viscous oil is diluted with ethanol and acetic acid, treated with 2-ethacrolein (19.5 g, 0.232 mol), heated at 70° C. for 6 hours and vacuum distilled at 60° C.
Abstract
Description
______________________________________ ##STR4## I X Y Z R ______________________________________ H CH.sub.3 H C.sub.2 H.sub.5 H CH.sub.2 OCH.sub.3 H CH.sub.3 H CH.sub.2 Cl H C.sub.2 H.sub.5 H H H C.sub.2 H.sub.5 ______________________________________
Claims (16)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US07/803,855 US5225560A (en) | 1990-06-15 | 1991-12-09 | Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate |
Applications Claiming Priority (2)
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US07/538,862 US5124458A (en) | 1990-06-15 | 1990-06-15 | Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate |
US07/803,855 US5225560A (en) | 1990-06-15 | 1991-12-09 | Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate |
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US07/538,862 Continuation-In-Part US5124458A (en) | 1990-06-15 | 1990-06-15 | Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate |
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US07/803,855 Expired - Lifetime US5225560A (en) | 1990-06-15 | 1991-12-09 | Process for the preparation of dialkyl pyridine-2,3-dicarboxylate and derivatives thereof from dialkyl dichlorosuccinate |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070299264A1 (en) * | 2006-06-23 | 2007-12-27 | Huang Jim X | Method to control insects resistant to common insecticides |
US20080058394A1 (en) * | 2006-09-01 | 2008-03-06 | Dow Agrosciences Llc | Insecticidal N-substituted (2-substituted-1,3-thiazol)alkyl sulfoximines |
US20080194830A1 (en) * | 2007-02-09 | 2008-08-14 | Meyer Kevin G | Process for the preparation of 2-substituted-5-(1-alkylthio)alkylpyridines |
US20090023782A1 (en) * | 2007-07-20 | 2009-01-22 | Dow Agrosciences Llc | Increasing plant vigor |
US20090221424A1 (en) * | 2008-03-03 | 2009-09-03 | Dow Agrosciences Llc | Pesticides |
US20100056579A1 (en) * | 2004-04-08 | 2010-03-04 | Dow Agrosciences Llc | Insecticidal n-substituted sulfoximines |
US20100087666A1 (en) * | 2008-10-02 | 2010-04-08 | Munson James R | Triacylglycerol purification by a continuous regenerable adsorbent process |
US20100144803A1 (en) * | 2006-02-10 | 2010-06-10 | Loso Michael R | Insecticidal n-substituted (6-halooalkylpyridin-3-yl)-alkyl sulfoximines |
US20100168172A1 (en) * | 2006-11-08 | 2010-07-01 | Loso Michael R | Heteroaryl (substituted)alkyl n-substituted sulfoximines as insecticides |
US20100234398A1 (en) * | 2006-09-01 | 2010-09-16 | Dow Agrosciences Llc | Insecticidal n-substituted (heteroaryl)alkyl sulfilimines |
US20110200684A1 (en) * | 2007-05-01 | 2011-08-18 | Dow Agrosciences Llc | Synergistic pesticidal mixtures |
Citations (6)
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US4723011A (en) * | 1985-10-28 | 1988-02-02 | American Cyanamid Company | Preparation of substituted and disubstituted-pyridine-2,3-dicarboxylate esters |
US4758667A (en) * | 1986-02-10 | 1988-07-19 | Ciba-Geigy Corporation | Process for the preparation of 2-(imidazolin-2-yl)-3-pyridine- and -3-quinolinecarboxylic acids |
US4798619A (en) * | 1980-06-02 | 1989-01-17 | American Cyanamid Co. | 2-(2-imidazolin-2-yl)-pyridines and quinolines and use of said compounds as herbicidal agents |
US4871859A (en) * | 1988-03-02 | 1989-10-03 | Hoechst Celanese Corporation | Process for preparing pyridine carboxylic acid esters |
US4948896A (en) * | 1987-07-08 | 1990-08-14 | Daiso Co., Ltd. | Process for preparing pyridine-2,3-dicarboxylic acid compounds |
US5008392A (en) * | 1988-12-01 | 1991-04-16 | Wacker-Chemie Gmbh | Process for the preparation of pyridine-2,3-dicarboxylic acid esters |
-
1991
- 1991-12-09 US US07/803,855 patent/US5225560A/en not_active Expired - Lifetime
Patent Citations (6)
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US4798619A (en) * | 1980-06-02 | 1989-01-17 | American Cyanamid Co. | 2-(2-imidazolin-2-yl)-pyridines and quinolines and use of said compounds as herbicidal agents |
US4723011A (en) * | 1985-10-28 | 1988-02-02 | American Cyanamid Company | Preparation of substituted and disubstituted-pyridine-2,3-dicarboxylate esters |
US4758667A (en) * | 1986-02-10 | 1988-07-19 | Ciba-Geigy Corporation | Process for the preparation of 2-(imidazolin-2-yl)-3-pyridine- and -3-quinolinecarboxylic acids |
US4948896A (en) * | 1987-07-08 | 1990-08-14 | Daiso Co., Ltd. | Process for preparing pyridine-2,3-dicarboxylic acid compounds |
US4871859A (en) * | 1988-03-02 | 1989-10-03 | Hoechst Celanese Corporation | Process for preparing pyridine carboxylic acid esters |
US5008392A (en) * | 1988-12-01 | 1991-04-16 | Wacker-Chemie Gmbh | Process for the preparation of pyridine-2,3-dicarboxylic acid esters |
Cited By (39)
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---|---|---|---|---|
US20100076032A1 (en) * | 2004-04-08 | 2010-03-25 | Dow Agrosciences Llc | Insecticidal n-substituted sulfoximines |
US7897782B2 (en) | 2004-04-08 | 2011-03-01 | Dow Agrosciences Llc | Insecticidal N-substituted sulfoximines |
US7834188B2 (en) | 2004-04-08 | 2010-11-16 | Dow Agrosciences Llc | Insecticidal N-substituted sulfoximines |
US7829719B2 (en) | 2004-04-08 | 2010-11-09 | Dow Agrosciences Llc | Insecticidal N-substituted sulfoximines |
US7795456B2 (en) | 2004-04-08 | 2010-09-14 | Dow Agrosciences Llc | Insecticidal N-substituted sulfoximines |
US20100056579A1 (en) * | 2004-04-08 | 2010-03-04 | Dow Agrosciences Llc | Insecticidal n-substituted sulfoximines |
US20100056578A1 (en) * | 2004-04-08 | 2010-03-04 | Dow Agrosciences Llc | Insecticidal n-substituted sulfoximines |
US20100063136A1 (en) * | 2004-04-08 | 2010-03-11 | Dow Agrosciences Llc | Insecticidal n-substituted sulfoximines |
US8193364B2 (en) | 2006-02-10 | 2012-06-05 | Dow Agrosciences, Llc. | Insecticidal N-substituted (6-haloalkylpyridin-3-yl)-alkyl sulfoximines |
US8669278B2 (en) | 2006-02-10 | 2014-03-11 | Dow Agrosciences, Llc. | Insecticidal N-substituted (6-haloalkylpyridin-3-yl)alkyl sulfoximines |
US9012654B2 (en) | 2006-02-10 | 2015-04-21 | Dow Agrosciences Llc | Insecticidal N-substituted (6-haloalkylpyridin-3-yl)-alkyl sulfoximines |
US20100144803A1 (en) * | 2006-02-10 | 2010-06-10 | Loso Michael R | Insecticidal n-substituted (6-halooalkylpyridin-3-yl)-alkyl sulfoximines |
US8288422B2 (en) | 2006-02-10 | 2012-10-16 | Dow Agrosciences, Llc. | Insecticidal N-substituted (6-halooalkylpyridin-3-yl)-alkyl sulfoximines |
US8598214B2 (en) | 2006-02-10 | 2013-12-03 | Dow Agrosciences, Llc. | Insecticidal N-substituted (6-haloalkylpyridin-3-yl)-alkyl sulfoximines |
US20100179099A1 (en) * | 2006-02-10 | 2010-07-15 | Loso Michael R | Insecticidal n-substituted (6-halooalkylpyridin-3-yl)-alkyl sulfoximines |
US20070299264A1 (en) * | 2006-06-23 | 2007-12-27 | Huang Jim X | Method to control insects resistant to common insecticides |
US8183270B2 (en) | 2006-09-01 | 2012-05-22 | Dow Agrosciences, Llc | Insecticidal N-substituted (2-substituted-1,3-thiazol)alkyl sulfoximines |
US20100234398A1 (en) * | 2006-09-01 | 2010-09-16 | Dow Agrosciences Llc | Insecticidal n-substituted (heteroaryl)alkyl sulfilimines |
US8188292B2 (en) | 2006-09-01 | 2012-05-29 | Dow Agrosciences, Llc | Insecticidal N-substituted (heteroaryl)alkyl sulfilimines |
US20110060018A1 (en) * | 2006-09-01 | 2011-03-10 | Loso Michael R | Insecticidal n-substituted (2-substituted-1,3-thiazol)alkyl sulfoximines |
US7863303B2 (en) | 2006-09-01 | 2011-01-04 | Dow Agrosciences Llc | Insecticidal N-substituted (2-substituted-1,3-thiazol)alkyl sulfoximines |
US20080058394A1 (en) * | 2006-09-01 | 2008-03-06 | Dow Agrosciences Llc | Insecticidal N-substituted (2-substituted-1,3-thiazol)alkyl sulfoximines |
US8183268B2 (en) | 2006-11-08 | 2012-05-22 | Dow Agrosciences, Llc. | Heteroaryl (substituted)alkyl N-substituted sulfoximines as insecticides |
US8017788B2 (en) | 2006-11-08 | 2011-09-13 | Dow Agrosciences Llc | Heteroaryl (substituted)alkyl N-substituted sulfoximines as insecticides |
US20100173950A1 (en) * | 2006-11-08 | 2010-07-08 | Loso Michael R | Heteroaryl (substituted)alkyl n-substituted sulfoximines as insecticides |
US20100168172A1 (en) * | 2006-11-08 | 2010-07-01 | Loso Michael R | Heteroaryl (substituted)alkyl n-substituted sulfoximines as insecticides |
US8318946B2 (en) | 2007-02-09 | 2012-11-27 | Dow Agrosciences, Llc | Process for the preparation of 2-substituted-5-(1-alkylthio)alkylpyridines |
US20080194830A1 (en) * | 2007-02-09 | 2008-08-14 | Meyer Kevin G | Process for the preparation of 2-substituted-5-(1-alkylthio)alkylpyridines |
US20100168435A1 (en) * | 2007-02-09 | 2010-07-01 | Dow Agrosciences Llc | Process for the preparation of 2-substituted-5-(1-alkylthio)alkylpyridines |
US7709648B2 (en) * | 2007-02-09 | 2010-05-04 | Dow Agrosciences Llc | Process for the preparation of 2-substituted-5-(1-alkylthio)alkylpyridines |
US20110200684A1 (en) * | 2007-05-01 | 2011-08-18 | Dow Agrosciences Llc | Synergistic pesticidal mixtures |
US8349815B2 (en) | 2007-05-01 | 2013-01-08 | Dow Agrosciences, Llc | Synergistic pesticidal mixtures |
US20090023782A1 (en) * | 2007-07-20 | 2009-01-22 | Dow Agrosciences Llc | Increasing plant vigor |
US8445689B2 (en) | 2008-03-03 | 2013-05-21 | Dow Agrosciences, Llc. | Pesticides |
US20110077160A1 (en) * | 2008-03-03 | 2011-03-31 | Dow Agrosciences Llc | Pesticides |
US20090221424A1 (en) * | 2008-03-03 | 2009-09-03 | Dow Agrosciences Llc | Pesticides |
US8178685B2 (en) | 2008-03-03 | 2012-05-15 | Dow Agrosciences, Llc | Pesticides |
US20100087666A1 (en) * | 2008-10-02 | 2010-04-08 | Munson James R | Triacylglycerol purification by a continuous regenerable adsorbent process |
US8232419B2 (en) * | 2008-10-02 | 2012-07-31 | The Dallas Group Of America | Triacylglycerol purification by a continuous regenerable adsorbent process |
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